Novel silicon-deficient mullite (Al5.65Si0.35O9.175) single crystal nanowires were synthesized in large quantities on mica substrates assisted by the intermediate fluoride species. The nanowires have diameters in the range 50-100 nm and typical lengths of several microm. Aligned nanowires were observed at the substrate edge. The nanowires have strong photoluminescence (PL) emission bands at 310, 397, 452 and 468 nm.